Polyvalent alkylene imine esters and a process of preparing them



Patented May 13, 1952 STATES BDLYNALENT ALKYLENE IMINE EsfrEns Anna moon es in PREPARING THEM Herbert, Bastian, Frankfurt-on-the-Main-Hochst,

Germany; assig'nor "to Farbwerke Hoechst vor-- inalsMe'ister Lucius & Bruning, Frankfurt-on:

the-Main-Hochst,

Germany, a manufacturing and; trading organization under the laws of the Qontrol; Council and Allied High Com- Np Drawing. Application May 26, 1949, Serial No,

In Germany October 1,1948

13 Claims. (01. 260-239) The present invention relates to polyvalent atlil zylene imineesters 'and a" process or preparing "'I have found that new polyvalent a,;3-alkylene imine compounds may be obtained by addition 5 of 'chg-alk'yleri'e imines t d,B- olfine' carboxylic acid esters ofpolyhydiicj alcohols.

Suitable agfi-ole fine 'carboxylic acid esters are,

for n staiieef he" crotonic acid'esters ofthe folg compoundsi ethyleneglvcol, propylene 1 glycol; 1,3-"anq' i.4-butylene "glycol, 1.6-hex'amethylene glycol, dihydroxy'diethyl"ether, dihydrdziyidjthyl sumdggmcero 1.3,5-hexanetriol, pentaerythrite orth'e like. -Instead of the crot'ofiic' acid esters there mayalso" be used theesters of the polyhydric alcohols of the following e43 olefine carboxylic acids: acrylic acid, methacrylic acid, tielic acid, afl-d me v ac y ic. a id it-W crotonic. acid, sorbic acid, a-cyansorbic acid, cinnamm ac d the k AS fi' g l i g .1. P3 1 h m t n d. efii t l tihy liimi t i 1-??12 site are??? the temple (JJHFJTQH awut lsne time oi the ,CH CH N11 315 OHallgdimethylethylene imine of the formula 40 /0 oHi"l -'NH ilzbi rlethrlem, at the armtl Irma-1 and other 1.2-alkylene imines which, for instance,

2 may be obtained by reaction of C-allgylethanolimine sulfuric acid esters with aqueous solutions of alkaline hydroxides.

According to the reactivity of1 the olefinic double bonds the addition takes place already at o e re. or t s veer-sta t t eat the components for a shorter or longer time at an elevated temperature. In some cases, the application of solvents or diluents may be advantageous. It is often advisable t'o'efiecjt the addition with an excess of a,/3-alkylene imine which, at the same time, serves as diluent. Thereby, the reaction is terminated more quickly and the excess of alkylene imine may easily be recovered by distilling. I

In case of compounds of particularly slow reactivity, the use of catalysts may be of advantage. There enter into'question' only neutral or alkaline catalysts, for instance, metal salts of saturated or unsaturated carboxylic acids, alcoholates such as sodium methylate, aluminium ethylate, furthermore, sodium arriide or the like.

According to the present invention compounds with several functional groups are obtained which correspond to the following general formula:

I R O-C O-R1N/ 1 Q E a wherein R stands for a polyvalent organic radical, especially'for an aliphatic hydrocarbon radical, the carbon chain of which may be interrupted by oxygen or' sulfur, R1 stands for a lowmolecular aliphatic, araliphatic or isocyclic hydrocarbon radical, R2, R3, and R4 stand for hydrogen or low-molecular alkyl radicals and n is an integer from 2 to 4. The most interesting of these compounds are those with two functional groups which correspond to the formula:

-34 wherein R, R1, R2, R3, and R4 have the E-Q J i meaning." Com'poundsdhe functional groupsnf which derive from ethylene imine are of particular importance.

The following compounds may be prepared according to this invention: the product obtained by condensation of ethylene imine with the reaction product of crotonic acid and ethylene glycol which corresponds to the following formula:

CH1 CH2 Ca Ha H: CH2

In the above formula, the group Compounds with 3 or 4 functional groups are derived correspondingly from Glycerol=HO-CH -(EEP-CH -OH labile alkylene imine ring they have a high stability which is shown, for instance, by the fact that the may be heated to 200 C. without changing.

The new alkylene imine esters may be used for various purposes, for instance, in the industries of textiles, plastics and varnishes.

The following examples serve to illustrate the invention but they are not intended to limit it thereto, the parts being by weight unless stated otherwise:

(1) 198 parts of acrylic acid 1.3-butylene ester (prepared from 2 mols of acrylic acid chloride and 1 mol of 1.3-butylene glycol) are slowly introduced into parts of ethylene imine, while stirring. By cooling with ice water, care is taken that the reaction heat will be removed. The whole isallowed to stand at room temperature for 24 hours and, subsequently, the bias-ethylene imino propionic acid-1.3-butylene ester, obtained with aquantitative yield and corresponding to the following formula:

is distilled under reduced pressure. It boils at 153 C. under a mercury pressure of 0.1 mm. The compound is easily soluble in water and the usual solvents.

(2) 198 parts of ethylene biscrotonate (prepared from 2 mols of crotonic acid and 1 mol of ethylene glycol) and 86 parts of ethylene imine are mixed intimately. The temperature rises nearly up to the boiling point. As soon as the heat tune decreases, the mixture is heated at 100 C. for 24 hours. Except for a small part, the ethylene imine has been fixed to the crotonic acid ester. The bis-p-ethylene imino butyric acid ethylene ester obtained which corresponds to the following formula:

CH1 l N-CH-CH2-C O-Q-OHz-CHz-O-C OCHzCH-N 2 Ha He CH2 boils at a temperature between C. and C. under a mercury pressure 0.5mm.

(3) 452 parts of lA-butylene biscrotonate (prepared from 2 mols of crotonic acid and 1 mol of 1.4-butylene glycol) and 258 parts of ethylene imine are intimatelymixed. 2 parts of sodium methylate are added and the whole is heated under reflux 75C. for .48 hours on the waterbath. By a suitable closing device the carbonic acid'of the air is excluded from the reaction mixture. When the heating on the water-bath is terminated, a test portion must be miscible with water to a clear solution. This being the case, the excess of ethylene imine is distilled off and OH the ethylene imine ester which has been formed 1. a.5=hexanetno1=H0-CHlCH1?H-(3H,-GH 60 is distilled under reduced pressure. The bis-B- OH H ethylene imino butyric acid 1.4-butylene ester and of the formula on, on, i N-CH-CH:-C O'-O--CHaCHr-CHz-CHa-C o-oorno -N H: H: H: (1E1 112- distils over at between 162 C. and 165 C. under CHPOH a mercury pressure of 0.2 mm.; it is obtained y n e= CHrLOH with a nearly quantitati ve yield as a color- CH O 70 less liquid which crystallizes on standing for a The alkylene imine esters obtainable according to this invention are for the major part oily compounds which are easily soluble in nearly all solvents. It is surprising that in spite of the prolonged period of time; the crystallization may be accelerated by the introduction of a crystal nucleus.

(4) While stirring and cooling, 1'72 parts of ethylene imine'a're caused to run into 296 parts of glycerol crotonate (prepared from 1 mol of glycerolandB mols of crotonic acid). The whole qv gdbu assume. s-ia-etn lene m ne c. a idii-digl cclr sten OI; he fprmlllei Namesa eo o-cm cm-o-om om-o-co-cm-cn-n o l H an: on,

a feebly. yellow oiliisoibtained with an is allowed to standgfor 24" hours at room temperature and the excess of ethylene imine is distilled" oif. The triethylene imine ester thus obtained which corresponds to the formula:

is a nearly colorless oily liquid which is miscible with water to a clear solution and which may excellent yield and in a. very pure state.

I claim:

t. The process which comprisesre'acting ethylene imine with ethylene-bis-crotonate.

2. The process which comprises reacting ethylene imine with 1,4-butylene-bis-crotonate.

3. The process which comprises reacting ethylene imine with diethylene glycol-bis-crotonate.

4. The products of the general formula wherein R stands for a radical having from 2 to 4 valences selected from the group consisting of polyvalent aliphatic hydrocarbon radicals, polyvalent aliphatic hydrocarbon radicals the chain of which is interrupted by oxygen and polyvalent aliphatic hydrocarbon radicals the chain of which is interrupted by sulfur, R1 stands for a low molecular aliphatic hydrocarbon radical, R2, R3, R4 stand for members of the group consisting of hydrogen and low molecular alkyl radicals, and n means an integer ranging from 2 to 4. 5. The compound of the formula CH: CH:

H H 40 on, on, l N-CHCH2C o-o-cm-om-o-c O-GHz-CHN l -cH-cm-c O-O-CHa-CHz-O-C OCHzCH-.N l

H: CH: H3 H2 H2 H3 H3 H2 boils at between 140 C. and 143 C. under a pres- 6. The compound of the formula CH2 CH2 N-cH-cmo OOCHzCHz-C Hicm-0-o O-CH2CHN l a H: H: H2 sure of 0.1 mm. mercury. It constitutes a color- 7. The compound of the formula CH: CH:

-CH-OH;--OOOCH1CHiOCH1CH:-OC0--CHz-CHN l H2 Ha Ha H2 less oily compound which is easily soluble in cold water. Even by feebly heating the aqueous solution, the compound separates in the form of an oil but, on cooling, dissolves again to a clear solution. It is remarkable that the reaction of the aqueous solution, as with all these compounds, is alkaline to delta paper and not alkaline to phenolphthalein.

(6) 242 parts of diethylene glycol-biscrotonate, prepared by esterification of p, 8'-dihydroxydiethylether and crotonic acid, are intimately mixed with 129 parts of ethylene imine and the whole is heated for 24 hours at 70 C.-80 C. When the reaction is performed in an apparatus without over-pressure, a suitable closing device must be provided which prevents the carbonic acid of the air from entering into the reaction mixture. When a test portion taken from the mixture is soluble in cold water or dilute hydrochloric acid to a clear solution, the addition of ethylene imine is finished. The excess of ethylene imine i re- 8. The process which comprises reacting an afi-alkylenimine with an ester of a low molecular aliphatic hydrocarbon mono-carboxylic acid containing an olefinic bond in a,/3-pOSitiDn and an alcohol having from 2 to 4 hydroxy groups selected from the group consisting of polyvalent aliphatic hydrocarbon alcohols, polyvalent aliphatic hydrocarbon alcohols whose carbon chain is interrupted by oxygen and polyvalent aliphatic hydrocarbon alcohols whose carbon chain is interrupted by sulfur. V

9. The products as claimed in claim 4, wherein R stands for a divalent lower alkylene radical, R2. R3, R4 each stand for hydrogen, and n=2..

10. The products as claimed in claim 4, wherein R stands for a divalent lower alkylene radical, R1 stands for an isopropylene group, R2, R3, R4 each stand for hydrogen, and 12:2.

11. The process as claimed in claim 8 wherein the alcohol is a divalent lower alkylene alcohol.

7 12. The processas, claimed in claim 8 wherein the afi alkylenlmine is ethylene'imine and the alcohol is a divalent lower alkylene alcohol.

13. The process'as claimed in claim 8 wherein the aliphatic mono-carboxylic acid is crotonlc acid, the a,;8-alkylenimine is ethylene imine and the alcohol is a divalent lower alkylene alcohol.

HERBERT BESTIAN.

REFERENCES CITED The following references are of record in the file of thisop'atent: V

8 V UNITED STATES PATENTS Number Name Date 2,222,208 Ulrich Nov. 19, 1940 r 2,265,416 Bestian Dec. 9, 1941 3 2,272,489 Ulrich Feb. 10, 1942 Ulrich Aug. 14, 1945 OTHER. REFERENCES 7 10 Hackhs Chemical Dictionary by Grant, 3rd ed., 7 1944, The Blakiston Company, Phila., Pa., p. 333. 

4. THE PRODUCTS OF THE GENERAL FORMULA 